Polyhalo ethyl-and polyhalo vinyl-dithioethyl carbonates and thio carbonates

ABSTRACT

Compounds are prepared having one of the formulas   WHERE A is selected from the group consisting of di to tetrahaloethyl and di to trihalovinyl; B is selected from the group consisting of hydrogen and -CH2OH; D is selected from the group consisting of hydrogen and   E is selected from the group consisting of hydrogen and   G is selected from the group consisting of hydrogen and   N IS 0 OR 1, X is selected from the group consisting of oxygen and sulfur except that when n is 0 in formula (2) X must be oxygen; Q is halogen; R1 is selected from the group consisting of alkyl, phenyl, lower alkyl phenyl, halo lower alkyl, halophenyl, naphthyl, lower alkyl naphthyl and lower alkyl halophenyl; R2 and R3 individually are the same as R1 or hydrogen with the proviso that not more than one of R2 and R3 is hydrogen and collectively together with the adjacent nitrogen atom form a five to six membered heterocyclic ring having up to 1 oxygen atom therein; R4 is R1 or OR PHENYL ETHYLENE OR HALOPHENOXYMETHYL HAVING UP TO 3 HALOGENS AND UP TO 1 METHYL GROUP ON THE AROMATIC RING; K is selected from the group consisting of   J is selected from the group consisting of hydrogen and ASSCH2CH2-; m is an integer from 0 to 2 inclusive, and all halogen atoms in the compounds have an atomic weight of 35 to 80. The compounds are useful as herbicides, fungicides, nematocides, defoliants and desiccants. 1,2,2-trichloroethyl-dithioethyl-2&#39;&#39;methyl-4&#39;&#39;-chlorophenoxy acetate is a particularly effective herbicide.

llnited States Patent Emerson et al.

[54] POLYHALO ETHYL-AND POLYHALO VINYL-DITI-IIOETHYL CARBONATES AND THIO CARBONATES [72] Inventors: Carl D. Emerson, Kansas City, Mo.; Paul C. Aichenegg, Prairie Village, Kans.

[73] Assignee: Baychem Corporation, New York,

22 Filed: March 27,1969

21 App1.No.: 811,233

Related US. Application Data [60] Division of Ser. No. 757,487, Sept. 4, 1968, which is a continuation-in-part of Ser. No. 560,125, June 24, 1966, abandoned.

[52] US. Cl. ..260/463, 260/247.1, 260/293.85, 260/326.3, 260/326.82, 260/399, 260/455 A,

260/455 B, 260/455 R, 260/469, 260/471 C,

260/473 C, 260/476 R, 260/475 R, 260/475 P, 260/482 B, 260/482 C, 260/485 J,

260/488 H, 260/488 J, 260/488 R, 260/608,

[51] Int. Cl...C07c 149/12, C070 154/00, AOln 9/12 [58] Field of Search .i ..260/455 B, 463

[56] References Cited UNITED STATES PATENTS 3,141,045 7/1964 Aichenegg et al .260/608 3,174,897 3/1965 Aichenegg et al ..424/366 3,203,996 8/1965 Moore ..260/608 Primary Examiner--Lewis Gotts Assistant Examiner-Diana Rivers Attorney-Cushman, Darby & Cushman [57] ABSTRACT Compounds are prepared having one of the formulas (1) A-S s ompnon AS s CHg(|3HOC(X)nR4 D (3) (AS s omomo o =X v 4 x R H 2 11-8 s CHzC|1HOC-N nematocides', defoliants [151 3,683,000 Aug. 8, 1972 and ( A sSCH2CHz-K where A is selected from the group consisting of di to tetrahaloethyl and di to trihalovinyl;

B is selected from the group consisting of hydrogen and CH OH;

D is selected from the group consisting of hydrogen and E is selected from the group consisting of hydrogen and -CH2O ("z-N a G is selected from the group consisting of hydrogen and i -CH;O CQ n is 0 or 1,

X is selected from the group consisting of oxygen and sulfur except that when n is 0 in formula (2) X must be oxygen;

Q is halogen;

R is selected from the group consisting of alkyl, phenyl, lower alkyl phenyl, halo lower alkyl,

halophenyl, naphthyl, lower alkyl naphthyl and J is selected from the group consisting of hydrogen and ASSCH CH m is an integer from 0 to 2 inclusive, and all halogen atoms in the compounds have an atomic weight of 35 to 80.

The compounds are useful as herbicides, fungicides,

and desiccants. 1,2,2- trichloroethyl-dithioethyl-2'-methyl-4'-chlorophenoxy acetate is a particularly effective herbicide.

7 Claims, No Drawings POLYHALO ETHYL-AND POLYHALO VINYL- DITHIOETHYL CARBONATES AND THIO CARBONATES This application is a division of Ser. No. 757,487, filed Sept. 4, 1968, which application is a continuationin-part of Ser. No. 560,125, filed June 24, 1966 and now abandoned.

The present invention relates to novel polyhalo disulfide alcohols and derivatives thereof.

It is an object of the present invention to prepare novel polyhalo ethyl or vinyl'disulfide alcohols and derivatives thereof.

Another object is to prepare novel polyhalo ethyl or vinyl dithioethyl chloroformate group containing organic compounds which are useful as intermediates in making other compounds.

A further object is to prepare novel fungicides.

An additional object is to prepare novel nematocides.

Yet another object is to prepare novel defoliants and desiccants.

A still further object is to prepare post emergent herbicides.

Still further objects and the entire scope of applicability of the present invention will become apparent from the detailed description given hereinafter; it should be understood, however, that the detailed description and specific examples, while indicating preferred embodiments of the invention, are given by way of illustration only, since various changes and modifications within the spirit and scope of the invention will become apparent to those skilled in the art from this detailed description.

It has now been found that these objects can be attained by preparing a compound having one of the following formulas:

(1)' ASSCHzCHOH A s s OHzCHO(X) R4 (A S 3 CH2CH20)2C =X AS s omcno-r/ A s s CHZOHO i-o, Cl and where A is selected from the group consisting of di to tetrahaloethyl and di to trihalovinyl;

B is selected from the group consisting of hydrogen and CH OH D is hydrogen or G is hydrogen or x -0H,0 o

n is 0 or 1;

X is oxygen or sulfur except that when n is 0 in formula ('2) X must be oxygen;

0 is halogen; I

R, is alkyl, phenyl, lower alkyl phenyl, phenyl ethylene, halo lower alkyl, halophenyl, naphthyl, lower alkyl naphthyl or lower alkyl halophenyl;

R and R, individually are the same as R, or hydrogen with the proviso that not more than one of R and R is hydrogen and collectively with the adjacent nitrogen atom form a five to six membered heterocyclic ring having up to 1 oxygen atom therein;

R is R, or

or phenyl ethylene or phenoxymethyl having up to 3 halogen atoms and up to 1 methyl group on the aromatic ring;

where J is hydrogen or ASSCH CH m is an integer from 0 to 2 inclusive and all halogen atoms in the compounds have an atomic weight of 35 to 80, i.e. are chlorine or bromine.

Preferably all halogen atoms are chlorine and preferably any alkyl group is a lower alkyl group, most preferably having one to four carbon atoms. The preferred compounds are those where A is trichloroethyl or dichlorovinyl.

The compounds of the present invention are useful as fungicides, nematocides, defoliants and desiccants, e.g. for cotton and beans, post emergent herbicides, pre-emergent herbicides, bactericides, etc.

The compounds of formula (1) also are useful in preparing the compounds of formulas (2), (3), (4), (5) and (6) and other compounds.

The compounds of formula (5) are useful in preparing the compounds of formula (2) which are carbonates or thiol carbonates and as intermediates in making other compounds.

The compounds of formula (1) are prepared by reacting the corresponding sulfenyl halides with the appropriate mercapto alcohol. As sulfenyl halides there can be used 1,2,2-trichloroethyl sulfenyl chloride, 2,2,2-trichloroethyl sulfenyl chloride, 2,2- dichloroethyl sulfenyl chloride, 1,2-dichloroethyl sulfenyl chloride, l,2,2,2-tetrachloroethyl sulfenyl chloride, l,2,2-tribromoethyl sulfenyl chloride, 2,2-dichlorovinyl sulfenyl, chloride, 1,2-dichlorovinyl sulfenyl chloride, 2,2-dibromovinyl sulfenyl bromide,- 1,2,2- trichlorovinyl sulfenyl chloride.

chlorophenoxyacetyloxy) propyl disulfide, 2,2,2- trichloroethyl-2 ,3 '-di (2 -methyl-4 '-chlorophenoxyacetyloxy) propyl disulfide, 2,2-dichlorovinyl-2',3'-di (2"-methyl-4"-chlorophenoxyacetyloxy) propyl disulfide, l ,2-dichlorovinyldithioethyl-2-met.hyl-4'- chlorophenoxyacetate, 1 ,2,2,2-tetrachloroethyldithioethyl-2'-methyl-4-chlorophenoxy-acetate,

l ,2,2,2-tetrachloroethyldithioethyl-2 ,4'- dichlorophenoxyacetate, l,2,2,2-tetrachloroetl'iyldithioethyl 2,4,5 '-trichlorophenoxyacetate.

The compounds of formula (2) which are carbonates, thiol carbonates and dithiocarbonates are made by one of the following three methods:

II (a) reacting the appropriate alcohol of formula (1) with the appropriate alkyl or aryl chloroformate;

II (b) reacting the appropriate disulfide chloroformate of formula (5) with the appropriate alkyl alcohol, aryl alcohol, phenol or mercaptan or xanthate;

II (c) reacting the appropriate polyhaloethyl or polyhalovinyl sulfenyl halide, e.g. any of those previously set forth, with a mercaptocarbonate.

Examples of suitable chloroformates for reaction II (a) are methyl chloroformate, ethyl chloroformate, propyl. chloroformate, butyl chloroformate, isobutyl chloroformate, hexyl chloroformate, cyclohexyl chloroformate, octyl chloroformate, dodecyl chloroformate, phenyl chloroformate, 4-methylphenyl chloroformate, 4-chlorophenyl chloroformate, anaphthyl chloroformate, B-naphthyl chloroformate, 2- bromophenyl chloroformate, 2ichloroethylchloroformate, 3-butylphenyl chloroformate, methyl chlorothiol formate, ethyl chlorothiol formate, isopropyl chlorothiol formate, butyl chlorothiol formate, amyl chlorothiol formate, phenyl chlorothiol formate, 2,4- dimethylphenyl chlorothiol formate, B-naphthyl chlorothiol formate.

Examples of suitable alcohols, phenols, mercaptans and xanthates for use in reaction 11 (b) are methyl alcohol, ethyl alcohol, isopropyl alcohol, propyl alcohol, butyl alcohol, sec. butyl alcohol amyl alcohol, cyclohexyl alcohol, hexyl alcohol, octyl alcohol, isooctyl alcohol, dodecyl alcohol, phenol, m-cresol, o-cresol, p-cresol, benzyl alcohol, p-chlorophenol, d-naphthol, fi-naphthol, a-methyl-fi-naphthol, methyl mercaptan, ethyl mercaptan, propyl mercaptan, dodecyl mercaptan, butyl mercaptan, cyclohexyl mercaptan, amyl mercaptan, benzyl mercaptan, thiophenol, p-thiocresol, anaphthyl mercaptan, ethylene chlorohydrin, propylene chlorohydrin, potassium ethyl xanthate, sodium ethyl xanthate, potassium butyl xanthate, potassium methyl xanthate. The disulfide chloroformates which can be employed are set forth infra.

Examples of suitable mercaptocarbonates for reaction II (c) are ethyl-2-mercaptoethyl carbonate, methyl-2-mercaptoethyl carbonate, propyl-Z-mercaptoethyl carbonate, butyl-Z-mercaptoethyl carbonate, hexyl-2-mercaptoethyl carbonate, cyclohexyl-Z-mercaptoethyl carbonate, phenyl-Z-mercaptoethyl carbonate, p-tolyl-2-mercaptoethyl carbonate, 0:- naphthyl-2-mercaptoethyl carbonate.

Examples of carbonates, thiol carbonates and dithiocarbonates within formula (2) are l,2,2- trichloroethyl dithioethyl-ethyl carbonate, 2,2,2- trichloroethyl dithioethyl-ethyl carbonate,

'trichloroethyl dithioethyl-dodecyl trichloroethyl dithioethyl-phenyl carbonate, 2,2,2- trichloroethyl dithioethyl-phenyl carbonate, 2,2- dichlorovinyl dithioethyl-ethyl carbonate, 2,2-

dichlorovinyl dithioethyl-methyl carbonate, 2,2- dichlorovinyl dithioethyl-methyl carbonate, 2,2,2- trichloroethyl dithioethyl-propyl carbonate, 1 ,2,2- trichloroethyl dithioethyl-isopropyl carbonate, 2,2- dichlorovinyl dithioethyl-propyl carbonate, 1 ,2,2- trichloroethyl dithioethyl-butyl carbonate, 2,2,2- trichloroethyl dithioethyl-butyl carbonate, 2,2- dichlorovinyl dithioethyl-butyl carbonate, 1 ,2,2-

trichloroethyl dithioethyl sec. butyl carbonate, 2,2,2- trichloroethyl dithioethyl-amyl carbonate, 2,2- dichlorovinyl dithioethyl-amyl carbonate, l,2,2- trichloroethyl dithioethyl-hexyl carbonate, 2,2- dichlorovinyl dithioethylcyclohexyl carbonate, 2,2,2- trichloroethyl dithioethyl-cyclohexyl carbonate, l,2,2- trichloroethyl dithioethyl-octyl carbonate, 2,2,2- carbonate, 2,2- dichlorovinyl dithioethyl-dodecyl carbonate, l,2,2- trichloroethyl dithioethyl-p-tolyl carbonate, 2,2,2- trichloroethyl dithioethyl-o-tolyl carbonate, 2,2- dichlorovinyl dithioethyl-m-tolyl carbonate, l,2,2- trichloroethyl dithioethyl-p-butylphenyl' carbonate, 2,2,2-trichloroethyl dithioethyl-B-naphthyl carbonate, 2,2-dichlorovinyl dithioethyl-a-naphthyl carbonate, 1,2,2-trichloroethyl dithioethyl-2'-chloroethyl carbonate, l,2,2-trichloroethyl dithioethyl-p-chlorophenyl carbonate, 2,2,2-tribromoethyl dithioethyl-obrornophenyl carbonate, 2,2-dichlorovinyl dithioethylm-chlorophenyl carbonate, 2,2,2-trichloroethyl dithioethyl-2',4'5'-trichlorophenyl carbonate, 2,2- dichlorovinyl dithioethyl-2'-methyl-4-chlorophenyl carbonate, 1 l ,2-trichloro-3 ,4-dithiaheptane-6,7-di (ethyl carbonate), 1 ,1 1-trichloro-3 ,4-dithiaheptane- 6,7-di (methyl carbonate), l,l-dichloro3,4-dithiaheptene-1,6,7di (ethyl carbonate), l,l,2-trichloro-3,4- dithiaheptane-6,7-di (propyl carbonate), 1,1,1- trichloro-3,4-dithiaheptane-6,7-di (butyl carbonate), 1 l -dichloro-3,4-dithiaheptenel ,6,7-di (propyl carbonate l l ,2-trichloro-3 ,4-dithiaheptane-6,7-di (phenyl carbonate), 1 ,1 ,2-trichloro-3,4-dithiaheptane- 6,7-di (phenyl carbonate), l,l-dichloro-3,4-dithiaheptene-l,6,7-di (phenyl carbonate), l,l-dichloro-3,4- dithiaheptenel,6,7-di (a-naphthyl carbonate), 1,1,1- trichloro-3,4-dithiaheptane-6,7-di (p-chlorophenyl carbonate), l,2,2-trichloroethyl dithioethyl-S-ethyl thiol carbonate, 2,2,2-trichloroethyl dithioethyl-S-ethyl thiol carbonate, 2,2-dichlorovinyl dithioethyl-S-ethyl thiol carbonate, 2,2,2-tribromoethyl dithioethyl-S- ethyl thiol carbonate, 2,2-dibromovinyl dithioethyl-S- ethyl thiol carbonate, l,2,2-trichloroethyl dithioethyl-S methyl thiol carbonate, 2,2-dichlorovinyl dithioethyl-S- methyl thiol carbonate, 2,2,2-trichloroethyl dithioethyl-S-propyl thiol carbonate, 1,2,2-trichlorovinyl dithioethyl-S-amyl thiol carbonate, l,2,2,2- tetrachloroethyl dithioethyl-S-hexyl thiol carbonate,

1,2,2-trichloroethyl dithioethyl-S-butyl thiol carbonate, 2,2,2-trichloroethyl dithioethyl-S-butyl thiol carbonate, 2,2-dichlorovinyl dithioethyl-S-butyl thiol carbonate, 1,2,2-trichloroethyl dithioethyl-S-octyl thiol carbonate, 1,2,2-trichloroethyl dithioethyl-S-phenyl thiol carbonate, 2,2,2-trichloroethyl dithioethyl-S- phenyl thiol carbonate, 2,2-dichlorovinyl dithioethyl-S- phenyl thiol carbonate, 1 ,2,2-trichloroethyl dithioethyl-S-o-tolyl thiol carbonate, 2,2-dichlorovinyl dithioethyl-S-p-tolyl thiol carbonate, 2,2,2- trichloroethyl dithioethyl-S-a-naphthyl thiol carbonate, 2,2-dichlorovinyl dithioethyl-S-2',4'- dichlorophenyl thiol carbonate, 2,2-dichlorovinyl dithioethyl-S-Z-chloroethyl thiol carbonate, 1,1,2- trichloro-3,4-dithiaheptane-6,7-di (ethyl thiol carbonate), 1,1,l-trichloro-3,4-dithiaheptane-6,7-di (ethyl thiol carbonate), 1,1-dichloro-3,4-dithiaheptene-1,6,7-di (ethyl thiol carbonate), 1,1,1-trich1oro- 3,4-dithiaheptane-6,7-di (methyl thiol carbonate), 1,1- dichloro-3,4-dithiaheptene-l,6,7-di (methyl thiol carbonate), l ,1 I-trichloro-3,4-dithiaheptane-6,7-di (butyl thiol carbonate), l,l-dichloro-3,4-dithiaheptene- 1,6,7-di (Butyl thiol carbonate), 1,1,1-trichloro-3,4- dithiaheptane-6,7-di (phenyl thiol carbonate), 1,1- dichloro-3,4-dithiaheptene-1,6,7-di (phenyl thiol carbonate), 1 ,1,2-trichloro-3,4-dithiaheptane-6J-di (2'- chloro-4'-methylphenyl thiol carbonate), 1,1-dichloro- 3,4-dithiaheptene-1,6,7-di (B-naphthyl thiol carbonate), 1,2,2-trichloroethyl dithioethyl-S-ethyl dithio carbonate, 2,2,2-trichloroethyl dithioethyl-S-ethyl dithio carbonate, 2,2-dichlorovinyl dithioethyl-S-ethyl dithio carbonate, 1,2-dichlorovinyl dithioethyl-S-ethyl dithio carbonate, 2,2,2-tribromoethyl dithioethyl-S- ethyl dithio carbonate, 2,2-dibromovinyl dithioethyl-S- ethyl dithio carbonate, 1,2,2-trichloroethyl dithioethyl- S-methyl dithio carbonate, 2,2-dichlorovinyl dithioethyl-S-methyl dithio carbonate, 2,2- trichloroethyl dithioethyl-S-propyl dithio carbonate, 1,2,2-trichlorovinyl dithioethyl-S-heptyl dithio carbonate, l,2,2,2-tetrachloroethyl dithioethyl-S-hexyl dithio carbonate, 1,2,2-trichloroethyl dithioethyl-S- butyl dithio carbonate, 2,2,2-trichloroethyl dithioethyl- S-butyl dithio carbonate, 2,2-dichlorovinyl dithioethyl- S-butyl dithio carbonate, 1,2,2-trichloroethyl dithioethyl-S-octyl dithio carbonate, 1 ,2,2- trichloroethyl-S-phenyl dithio carbonate, 2,2,2-

trichloroethyl dithioethyl-S-phenyl dithio carbonate, 2,2-dichlorovinyl dithio ethyl-S-phenyl dithio carbonate, 1,2,2-trichloroethyl dithioethyl-S-p-tolyl dithio carbonate, 2,2-dichlorovinyl dithioethyl-S-o-tolyl dithio carbonate, 2,2,2-trichloroethyl dithioethyl-S-anaphthyl dithio carbonate, 2,2-dichlorovinyl dithioethyl-S-2,4-dichlorophenyl dithio carbonate, 2,2-dichlorovinyl dithioethyl-S-2-chloroethyl dithio carbonate, 1 1 ,2-trichloro-3 ,4-dithiaheptane-6,7-di (ethyl dithio carbonate), l,l,l-trichloro3,4-dithiaheptane-6,7-(ethyl dithio carbonate) l,l-dichloro-3,4- dithiaheptene(-l)-6,7-di (ethyl dithio carbonate), 1,1- trichloro-3,4-dithiaheptane-6,7-di (methyl dithio carbonate), l,1-dichloro-3,4-dithiaheptene-1,6,7-di (methyl dithio carbonate), l,l,1-trichloro-3,4- dithiaheptane-6,7-di (butyl dithio carbonate), 1,1- dichloro-3,4-dithiaheptene-l,6,7-di (butyl dithio carbonate), 1,1,1-trichloro-3,4-dithiaheptane-6,7- di(phenyl dithio carbonate), l,l-dichloro-3,4-

dithiaheptene-l,6,7-di (phenyl dithio carbonate), 1 ,1 ,2-trichloro-3,4-dithiaheptane 6,7-di 2'-chloro-4 methylphenyl dithio carbonate), l,1-dichloro-3,4- dithiaheptene- 1 ,6,7-di (oz-naphthyl dithio carbonate).

O-[B-(1,2,2-trichloroethyl dithio) ethyl]-S-[O-ethylthiocarboxyl] dithio carbonate, O-[B-(2,2,2- trichloroethyl dithio) ethyl]-S-[O-methyl -thiocarboxyl] dithio carbonate, O-[B-(2,2-dichlorovinyl dithio) ethyl] -S-[O-butyl-thiocarboxyl] dithio carbonate, 0- [B-( 1,2,2-trichloroethyl dithio) ethyl ]-S-[ O-phenylthiocarboxyl1dithio carbonate, O-[B-(2,2-dichlorovinyl dithio) ethylI-S-[O-phenyl-thiocarboxyl] dithio carbonate, O-[B-( 1,2,2-trichloroethyl dithio)ethyl]-S- [O-p-tolyl-thiocarboxyl] dithio carbonate.

The compounds of formula (3) are made by reacting the appropriate alcohol of formula (1) with the appropriate disulfide chloroforrnate of formula (5 Examples of compounds within formula (3) are bis- (l,2,2-trichloroethyl dithioethyl) carbonate, bis- (2,2,2-trichloroethyl dithioethyl) carbonate, bis-(2,2- dichlorovinyl dithioethyl) carbonate, 2-trichloroethyl dithioethyl)-(2,2-dichlorovinyl dithioethyl) carbonate, bis (1,2,2-tribromoethyl dithioethyl) carbonate, bis (1,2,2-trichloroethyl dithioethyl) thiocarbonate, bis (2,2-dichlorovinyl dithioethyl) thiocarbonate.

The compounds of formula (4) are made by one of the following methods:

III (a) reacting the appropriate alcohol of formula (1 with the appropriate alkyl, aryl or haloaryl isocyanate or isothiocyanate;

III (b) by reacting the appropriate alcohol of formula (1) with an appropriate carbamoyl halide, e.g. chloride or bromide;

III (e) by reacting the appropriate polyhaloethyl or polyhalovinyl disulfide chloroformate of formula (5) with the appropriate amount of a primary or secondary amine. 2 equivalents of amine are required for each equivalent of chloroforrnate.

Examples of suitable isocyanates for reaction III (a) are phenyl isocyanates p-tolyl isocyanate, m-tolyl isocyanate,:x-naphthyl isocyanate, 2-chlorophenyl isocyanate, 2,4-dichlorophenyl isocyanate, ethyl iso cyanate, propyl isocyanate, butyl isocyanate, hexyl isocyanate, cyclohexyl isocyanate, dodecyl isocyanate, 2- methyl-4-chlorophenyl isocyanate, phenyl isothiocyanate, o-tolyl isothiocyanate, ethyl isothiocyanate, methyl isothiocyanate, butyl isothiocyanate, B- naphthyl isothiocyanate.

Examples of suitable carbamoyl halides for reaction III (b) are dimethyl carbamoyl chloride, diethyl carbamoyl chloride, diethyl carbamoyl bromide, dipropyl carbamoyl chloride dibutyl carbamoyl chloride, dihexyl carbamoyl chloride, dicetyl carbamoyl chloride, diphenyl carbamoyl chloride, di (2-chlorophenyl) carbamoyl chloride, ethyl carbamoyl chloride, amyl carbamoyl chloride, phenyl carbamoyl chloride, di [3- naphthyl carbamoyl chloride.

Examples of suitable primary and secondary amines for reaction III (c) are methyl amine, ethyl amine, propyl amine, butyl amine, isopropyl amine, sec. butyl amine, amyl amine, hexyl amine, cyclohexyl amine, cetyl amine, isooctyl amine, dodecyl amine, aniline, otoluidine, p-toluidine, p-chloroaniline, mchloroaniline, a-naphthyl amine, B-naphthyl amine, amethyl-B-naphthyl amine, 2-methyl-4-chloroaniline,

piperidine, morpholine, Z-methyl piperidine, pyrrolidine, dimethyl amine, diethyl amine, allyl amine, dipropyl amine, din (isopropyl) amine, dibutyl amine, dihexyl amine di cyclohexyl amine, dioctyl amine, di lauryl amine ethyl propyl amine, N-methyl aniline, N- ethyl aniline, N-butyl aniline, diphenyl amine, ochloro-N-methyl aniline, 2,4,6-tn'chloroaniline, 2,4,6- tribromo aniline.

Examples of carbamates and thiocarbamates within formula (4) are 1,2,2-trichloroethyl dithioethyl N- methyl 'carbamate, 2,2,2-trichloroethyl dithioethyl-N- methyl carbamate, l,2,2,2-tetrachloroethyl dithioethyl N-methyl cal-bamate, 1,2-dichloroethyl dithioethyl N- methyl cal-bamate, 1,2,2-tribromoethyl dithioethyl-N- methyl carbamate, 2,2-dichlorovinyl dithioethyl-N- methyl carbamate, 1,2-dichlorovinyl dithioethyl-N- methyl cal-bamate, 2,2-dibromovinyl dithioethyl-N- methyl carbamate, 1,2,2-trichloroethyl dithidethyl-N- ethyl carbamate, 2,2,2-trichloroethyl dithioethyl-N- ethyl carbamate, 2,2-dichlorovinyl dithioethyl-N-ethyl carbamate, 1,2,2-trichloroethyl dithioethyl-N-propyl carbamate, 2,2,2-trichloroethyl dithioethyl-N-propyl carbamate, 2,2-dichlorovinyl dithioethyl N-propyl carbamate, 2,2,2-trichloroethyl dithioethyl-N-isopropyl carbamate, 1,2,2-trichloroethyl dithioethyl-N-ethyl carbamate, 2,2,2-trichloroethyl dithioethyl-N-ethyl carbamate, 2,2-dichlorovinyl dithioethyl-N-ethyl carbamate, 1,2,2-trichloroethyl dithioethyl-N-propyl carbamate, 2,2, dichlorovinyl' dithioethyl N-propyl carbamate, 2,2,2-trichloroethyl dithioethyl-N-isopropyl carbamate, 1,2,2-trichloroethyl dithioethyl-N-butyl carbamate, 2,2,2-trichloroethyl dithioethyl-N-butyl carbamate, 2,2-dichlorovinyl dithioethyl-N-butyl carbamate, 2,2-dichlorovinyl dithioethyl-N-sec butyl carbamate, 1,2,2-tichloroethyl dithioethyl N-amyl carbamate, 2,2-dichlorovinyl dithioethyl-N-amyl cal-bamate, 2,2,2-trichloroethyl-dithioethyl-N-hexyl cal-bamate, 2,2-dichlorbvinyl dithioethyl-N-hexyl carbamate, 1,2,2-trichloroethyl ditl'iioethyl-N-cyclohexyl caxbamate, 2,2-dichloroyinyl dithioethyl-N-cyclohexyl carbamate, 2,2,2-trichloroethyl dithioethyl-N-cetyl carbamate, 2,2-dichlorovinyl dithioethyl-N-isooctyl carbamate, 1,2,2-trichloroethyl dithiOethyl-N-dodecyl carbamate, 2,2-dichlorovinyl dithioethyl-N-dodecyl carbamate, 1,2,2-trichloroethyl dithioethyl-N-2'- chioroethyl carbamate, 1 ,2,2-trichloroethyl dithioethyl-N-phenyl carbamate, 2,2,2-triehloroethyl dithioethyl-N-phenyl carbamate, 2,2-dichlorovinyl dithioethyl-N-phenyl carbamate, 1,2,2-trichloroethyl dithioethyl-N-p-tolyl carbamate, 2,2,2-trichloroethyl dithioethyl-N-m-tolyl cal-bamate, 2,2-dichlorovinyl dithioethyl-N-o-tolyl carbarnate, 1,2,2-trichloroethyl dithioethyl-N-p-ethyl-phenyl carbamate, 2,2- dichlorovinyl dithioethyl-N-p-butylphenyl carbamate,

2,2,2-trichloroethyl dithioethyl-N-p-chlorophenyl carmorpholino carbamate, 2,2-dichlorovinyl dithioethylmorpholino can-bamate, 2,2,2-trichloroethyl dithioethyl-piperidyl carbamate, 2,2-dichlorovinyl dithioethyl piperidyl carbamate, 1,2,2-trichloroethyl dithioethyl pyrrolidyl carbamate, 2,2-dichlorovinyl dithioethyl pyrrolidyl carbamate, 1,2,2-trichloroethyl dithioethyl-N, N-dimethyl carbamate, 2,2,2- trichloroethyl dithioethyl-N, N-dimethyl carbamate, 2,2-dichlorovinyl dithioethyl-N, N-dimethyl carbamate, 1,2,2-trichloroethyl dithioethyl-N, N-diethyl carbamate, 2,2,2-trichloroethyl dithioethyl-N, N-diethyl carbamate, 2,2-dichlorovinyl dithioethyl-N, N-diethyl cal-bamate, 2,2-dibromovinyl dithioethyl-N, N-diethyl cal-bamate, 1,2-dichlorovinyl dithioethyl-N, N-diethyl cal-bamate, l,2,2,2-tetrachloroethyl dithioethyl-N, N- diethyl cam-bamate, 1,2-dichloroethyl dithioethyl-N, N- diethyl carbamate, 1,2,2-trichloroethyl dithioethyl-N- ethyl-N-propyl carbamate, 2,2-dichlorovinyl dithioethyl-N-ethyl-N-butyl carbamate, 1 ,2,2- trichloroethyl dithioethyl-N, N-dipropyl carbamate, 2,2,2-trichloroethyl dithioethyl-N, N-dipropyl carbamate, 2,2-dichlorovinyl dithioethyl-N, N-dipropyl carbamate, 1,2,2-trichloroethyl dithioethyl-N, N- diisopropyl carbamate, 2,2-dichlorovinyl dithioethyl- N, N-diisopropyl carbamate, 1,2,2-trichloroethyl dithioethyl-N, 'N-dibutyl caxbamate, 2,2,2- trichloroethyl dithioethyl-N, N-dihutyl cal-bamate, 2,2- dichlorovinyl dithioethyl-N, N-dibutyl cam-bamate, 2,2,2-trichloroethyl dithioethyl-N, N-di sec. amyl carbamate, 2,2-dichlorovinyl dithioethyl-N, N-diamyl carbamate, 1,2,2-trichloroethyl dithioethyl-N, N-dihexyl carbamate, 2,2-dichlorovinyl dithioethyl-N, N-dihexyl carbamate, 2,2,2-trichloroethyl dithioethyl-N, N- dicyclohexyl carbamate, 2,2-dichlorovinyl dithioethyl- N, N-dicyclohexyl cal-bamate, 1,2,2-trichloroethyi dithioethyl-N, N-diheptyl carbamate, 2,2-dichlorovinyl dithioethyl-N, 'N-diocytyl carbamate, 2,2,2- trichloroethyl dithioethyl-N, N-dilauryl cal-bamate, 2,2-dichlorovinyl dithioethyl-N, N-dilauryl carbarnate, 1,2,2-trichloroethyl dithioethyl-N, N-di-3'- chloropmpyl 'carbamate, 1 ,2,2-trichloroethyl dithioethyl-N phenyl N-methyl carbamate, 2,2,2- trichloroethyl dithioethyl-N phenyl N-ethyl carbamate, 1,2,2-trichloroethyl dithioethyl-N, N-diphenyl carbamate, 2,2-dichlorovinyl dithioethyl-N, N-diphenyl carbamate, 2,2-diehlorovinyl dithioethyl-N phenyl N- methyl carbamate, l,2,2-u'ichloroethyl dithioethyl-N- m-tolyl N-methyl carbamate, 2,2,2-trichloroethyl dithioethyl-No-tolyl N-ethyl carbamate, 2,2- dichlorovinyl dithioethyl-N-p-tolyl N-methyl carbamate, 1,2,2-trichloroethyl dithioethyl-N-p-butylphenyl N-methyl carbamate, 2,2-dichlorobinyl ditl'lioethyl-N- t-butylphenyl N-methyl carbamate, 1 ,2,2- trichloroethyl ditiioethyl-N -ochlorophenyl N-butyl carbamate, 2,2-dichlorovinyl dithioethyl-N 2,4',6'- trichlorophenyl N-methyl carbamate, 1,2,2- trichloroethyl dithioethyl-N-B-naphflxyl N-methyl carbamate, 2,2-dichlorovinyl dithioethyl-N-a-naphthyl N- methyl carbamate, 1,1,l-trichloro-3,4-dithiaheptane- 6,7-di (N-methyl carbamate), 1,1,l-trichloro-3,4-dithiaheptane6,7-di (N,N-dimethyl carbamate), 1,1,1- trichloro 3,4-dithiaheptane-6,7-di (N-ethyl carbamate), 1,1,l-trichloro-3,4-dithiaheptane-6,7-di (N,N- diethyl carbamate), 1,1 l -trichloro-3,4-dithiaheptane- 6,7-di (N, N-diethyl carbamate), l,1,2-trichloro-3,4-

dithiaheptane-6,7-di(N-ethyl carbamate), 1,1- dichloro-3,4-dithiaheptene(-1 )6,7-di (N-methyl carbamate), 1 l-dichloro-3 ,4-dithiaheptene(-1 6,7-di (N,N-dimethyl carbamate 1,1-dichloro-3 ,4- dithiaheptene(-l), 6,7-di (N-ethyl carbarnate), 1,1- dichloro-3,4-dithiaheptene-1,6,7-di (N,N-diethyl carbamate), 1, l ,2-trichloro-3,4-dithiaheptane-6,7-di (N- propyl carbamate), 1 ,1-dichloro-3,4-dithiaheptane(-1 )6,7-di (N, N-dipropyl carbamate), 1,1,l-trichloro- 3,4-dithiaheptane-6,7-di (N-butyl carbamate), 1,1,2- trichloro-3,4-dithiaheptane-6,7-di (N, N-dibutyl carbamate), 1,1-dichloro-3, 4-dithiaheptene-l,6,7-di (N- butyl carbamate), 1,1-dichloro-3,4-dithia.heptene- 1 ,6,7,-di (N,N-dibutyl carbamate), 1 1 1-trichloro-3,4- dithiaheptane-6,7-di (N-phenyl carbamate), 1,1,2- trichloro-3,4-dithiaheptane-6,7-di-(N, N-diphenyl carbarnate), 1 ,1-dichloro-3 ,4-dithiaheptene-1 ,6,7-di (N- phenyl carbamate), 1,1-dichloro3,4-dithiaheptene- 1,6,7-di (N,N-diphenyl carbamate), 1,1,l-trichloro- 3,4-dithiaheptane-6,7-di(N-B-naphthyl carbamate), 1,1-dichloro-3,4-dithiaheptane(-1), 6,7-di(N, N-dianaphthyl carbamate), 1 l ,2-trichloro-3,4-dithiaheptane-6,7-di (N, N-di-p-chlorophenyl carbamate), 1,1- dichloro-3,4-dithiaheptene(-1 )6,7-di(N-o-chlorophenyl carbamate), 1,2,2-trichloroethyl dithioethyl N- methyl thiocarbamate, 2,2-dichlorovinyl dithioethyl-N- methyl thiocarbamate, 2,2,2-trichloroethyl dithioethyl- N-ethyl thiocarbamate, l ,2,2-trichloroethyl dithioethyl-N, N-diethyl thiocarbamate, 2,2-dichlorovinyl dithioethyl-N-ethyl carbamate, 2,2-dichlorovinyl dithioethyl-N, N-diethyl thiocarbamate, 1,2,2- trichloroethyl dithioethyl-N, N-diisopropyl thiocarbamate, 2,2,2-tn'chloroethyl dithioethyl-N-butyl thiocarbamate, 1,2,2,-trichloroethyl dithioethyl-N, N-dibutyl thiocarbamate, 2,2-dichlorovinyl dithioethyl-N-butyl thiocarbamate, 2,2-dichlorovinyl dithioethyl-N, N- dibutyl thiocarbamate, 1,2,2-trichloroethyl dithioethyl- N-phenyl thiocarbamate, 2,2,2-trichloroethyl dithioethyl-N, N-diphenyl thiocarbamate, 2,2- dichlorovinyl dithioethyl-N-phenyl thiocarbamate, 2,2- dichlorovinyl dithioethyl-N, N-diphenyl thiocarbamate, l,2,2,-trichloroethyl dithioethyl N-p-tolyl thiocarbamate, 2,2,2-trichloroethyl-dithioethyl N,N-dip-tolyl thiocarbamate, 2,2-dichlorovinyl dithioethyl-N, N-di-p-tolyl thiocarbamate, 1,l,2-trichloro-3,4- dithiaheptane-6,7-di (n-methyl thiocarbamate), 1,1,1- trichloro-3,4-dithiaheptane-6,7-di (N, N-dibutyl thiocarbamate), 1,1-dichloro3 ,4-dithiaheptene( -1 )6,7- di (ethyl thiocarbamate), l,l,1-trichloro-3,4- dithiaheptane-6,7-di (N-phenyl thiocarbamate), 1,1- dichloro-3,4-dithiaheptene(-1),6,7-di (N, N-diphenyl thiocarbamate), l,l-dichloro-3,4-dithiaheptene(-1 ),6,7-di (N-p-tolyl thiocarbamate).

The compounds of formula (5) are made by reacting the appropriate alcohol of formula (1) with phosgene or thiophosgene.

Examples of compounds within formula (5) are: 1,2,2-trichloroethyl dithioethyl chloroformate, 2,2,2-

trichloroethyl dithioethyl chloroforrnate, 2,2- dichlorovinyl dithioethyl chloroformate, 2,2,2- tribromoethyl dithioethyl chloroformate, 2,2- dibromovinyl dithioethyl chloroformate, l ,2- dichlorovinyl dithioethyl chloroformate, 1 ,2- dichloroethyl dithioethyl chloroformate, 1 ,2,2,2- tetrachloroethyl dithioethyl chlorofonnate, 1 ,2,2-

trichloroethyl dithiopropyl-2,3, -di(chloroformate), 2,2,2-trichloroethyl dithiopropyl-2',3'-di (chloroformate), 2,2-dichlorovinyl dithiopropyl-2 ,3 '-di (chloroformate), 1,2,2,-trichloroethyl dithioethylthiono chloroformate, 2,2,2-trichloroethyl dithioethylthiono chloroformate, 2,2-dichlorovinyl dithioethylthiono chloroformate, l ,2,2-trichloroethyl dithiopropyl-2',3'di (thiono chloroformate), 2,2,2- trichloroethyl dithiopropyl-2,3'-di (thiono chloroformate), 2,2-dichlorovinyl dithiopropyl-2,3'-di (thiono chloroformate).

The compounds of formula (6) are prepared by reacting a dicarboxylic acid chloride or bromide with the appropriate monohydric alcohol within formula (1). If two moles of the alcohol are employed per mole of the dicarboxylic acid halide then a his ester is formed; with equimolar amounts of alcohol and dicarboxylic acid halide there is formed a half ester. The acid halide group in the latter case is then hydrolyzed to free acid with aqueous acid, e.g. hydrochloric acid or with a base such as sodium hydroxide or potassium hydroxide. If excess base is employed there is obtained the half salt, e.g. the sodium mono salt or potassium mono salt.

Examples of suitable dicarboxylic acid halides are oxalyl chloride, oxalyl bromide, malonylchlon'de, succinyl chloride, phthalyl chloride, tetrachlorophthalyl chloride, 4-chlorophthalyl chloride, fumaryl chloride, maleyl chloride, terephthalyl chloride, isophthalyl chloride.

Examples of compounds within formula (6) are bis- (2,2,2-trichloroethyl dithioethyl) oxalate, bis-(2,2-

dichlorovinyl dithioethyl) oxalate, bis-( 1,2,2,2- tetrachloroethyl dithioethyl oxalate, bis-( 1 ,2- dichloroethyl dithioethyl) oxalate, bis-( 1,2,2-

tribromoethyl dithioethyl) oxalate, bis-(1,2-dibromovinyl dithioethyl) oxalate, bis-(1,2,2-trichloroethyl dithioethyl) malonate, bis-(2,2,2-trichloroethyl malonate, bis-(2,2-dichlorovinyl dithioethyl) malonate, bis-(1,2,2-trichloroethyl dithioethyl) succinate, bis- (2,2,2-trichloroethyl dithioethyl) succinate, bis-(2,2- dichlorovinyl dithioethyl) succinate, bis-(1,2,2- trichloroethyl dithioethyl) malonate, bis-(2,2,2- trichloroethyl dithioethyl) maleate, bis-(2,2- dichlorovinyl dithioethyl) malonate, bis-(1,2,2- trichloroethyl dithioethyl) fumarate, bis-(2,2,2- tn'chloroethyl dithioethyl) fumarate, bis-(2,2- dichlorovinyl dithioethyl) fumarate, bis-(1,2,2- trichloroethyl dithioethyl) phthalate, bis-(2,2,2- trichloroethyl dithioethyl) phthalate, bis-(1,2,2- trichloroethyl dithioethyl) terephthalate, bis-(2,2,2- trichloroethyldithioethyl) terephthalate, bis-(2,2- dichlorovinyl dithioethyl) terephthalate, bis-(1,2,2- trichloroethyl dithioethyl) isophthalate, bis-(2,2- dichlorovinyl dithioethyl) isophthalate, bis-(2,2,2- trichloroethyl dithioethyl) tetrachlorophthalate, bis- (2,2-dichlorovinyl dithioethyl) tetrachlorophthalate, bis-(1,2,2-trichloroethyl dithioethyl) 4-chlorophthalate, mono-l,2,2-trichloroethyl dithioethyl oxalate, mono-2,2-dichloroethyl dithioethyl oxalate) mono- 2,2,2-tn'chloroethyl dithioethyl phthalate.

Unless otherwise indicated all parts and percentages are by weight.

METHODS OF PREPARATION I. Alcohols A. The saturated halo-disulfide alcohols of formula (1) are prepared generally by the dropwise addition of the chosen saturated sulfenyl halide in equimolar amounts to the appropriate mercapto-alcohol in an inert solvent. Such solvents include halohydrocarbons such as chloroform, carbon tetrachloride, and tetrachloroethane and hydrocarbons such as benzene, toluene, xylene, hexane, cyclohexane, petroleum ether, and aromatic naphtha. The reaction temperature in the examples below was 25 -3 C. which temperature was maintained by cooling with an ice-water bath completion of the reaction was determined by a negative reaction to XY-starch test paper. Isolation was accomplished by washing the reaction mixture with water drying and vacuum stripping.

B. The unsaturated halo disulfide alcohols within formula 1) were prepared by dehydrohalogenation of the saturated halo-disulfide alcohols with equivalent amounts of sodium ethoxide. In place of sodium ethoxide there can be used potassium ethoxide and other alcoholates having up to three carbon atoms, e.g. sodium methylate, sodium propylate, sodium isopropylate, potassium propylate. The reaction temperature was maintained at 2530 C. through cooling with an icewater bath. Dilution with water furnished the products as bottom oils.

lI. Carbonates, Thiol Carbonates, Dithiocarbonates The poly halo disulfide carbonates, thiol carbonates and dithiocarbonates within formulae (2) and (3) were prepared by three routes:

A. By the reaction of the polyhalo disulfide alcohol of formula l) with the chosen chloroforrnate, e.g. alkyl or aryl chloroformate. The alcohol and chosen chloroforrnate were mixed together and heated at a temperature between 85 and 120 C. (This temperature range can be varied if desired.) Reaction times normally were in the order of several hours and the reaction was completed on the disappearance of the hydroxyl absorption in the infrared spectrum analysis.

B. By the reaction of a polyhalo disulfide chloroformate of formula (5) and a chosen alcohol (e.g. alkyl or aryl alcohol) or mercaptan under the same general condition as described in II(A). in this reaction it was also observed that there was a shift to a lower frequency by the O O in the infrared spectrum of the formed carbonate. In some instances a tertiary base was used to force the reaction. Such tertiary bases include trialkyl amines such as trimethyl amine, triethyl amine, tripropyl amine, and triamyl amine, pyridine, dirnethyl aniline, diethyl aniline (and other tertiary aromatic amines) quinoline, a-picoline, B-picoline, lutidine.

C. By the reaction of a chosen polyhalo sulfenyl chloride with an appropriate mercapto carbonate under the same conditions as described in I(A).

III. Carbamates The polyhalo disulfide carbarnates of formula (4) were prepared by three routes:

A. By reaction of the chosen polyhalo disulfide alcohol of formula (1) with an appropriate organic isocyanate (or isothiocyanate), e.g. an alkyl or aryl isocyanate. The reagents are mixed and heated to 95 to 100 C. (This temperature can be varied somewhat if desired). The progress of the reaction was observed by periodic infrared scans. It was complete upon the disappearance of both the OH and N-C-O absorption.

B. By the reaction of a polyhalo disulfide alcohol with an appropriate carbarnoyl chloride. The two reactants were mixed and warmed at to 100 C. until the reaction was complete.

C. By the reaction of a polyhalo disulfide chloroformate of formula (5) with a primary or secondary amine. Two equivalents of the aminewere added dropwise at 2530C. to one equivalent of the chloroformate to furnish the product in a quantitative yield.

IV. Esters The esters of formula (2) (other than carbonates, thiolcarbonates and dithiocarbonates) and formula (6) were formed by reacting the polyhalo disulfide alcohol of formula (1) with an appropriate acyl chloride, e.g. an alkyl chloride or aryl chloride in an inert solvent at 30 to 80 C. Suitable solvents include hydrocarbons and halohydrocarbons such as those set forth in Method 1(A). The alcohol and acyl chloride are used in equimolar amounts except that when employing the acyl chlorides of dibasic acids there were used two moles of alcohol per mole of acyl halide to form the diester. V. The polyhalo disulfide chloroformates of formula (5) were prepared by two routes:

A. by allowing a mixture of the chosen halo disulfide alcohol of formula (1) and either phosgene or thiophosgene to stand at room temperature and atmospheric pressure, in an inert solvent (such as those set forth in Method 1(A), for several days until an infrared analysis shows the disappearance of the OH absorption and appearance of the absorption.

(B) By having the same mixture as in V(A) in a sealed tube at -90 C. for several hours. The degree of completeness of the reaction was determined by infrared analysis.

EXAMPLE 1 Compound 5598 1,2,2-trichloroethyl-B-hydroxyethyl disulfide 100 grams of 1,2,2-trichloroethyl sulfonyl chloride (0.5 M) reacted at 2530 C. with 39 grams of 2-mercaptoethanol in 50 ml. of CHCl as described in Method I-A furnished 1,2,2-trichloroethyl-B-hydroxyethyl disulfide in a 92 percent yield as a faintly yellow oil having n 1.5783.

EXAMPLE 2 Compound 5607 2,2,2-trichloroethyl-B-hydroxy-ethyl disulfide 100 grams of 2,2,2-trichloroethyl sulfenyl chloride (0.5 M) when reacted at 2530 C with 39.5 grams of Z-mercaptoethanol (0.506 M) in 50 ml. of CHCl as in example 1 resulted in a 95 percent yield of 2,2,2- trichloroethyl- -hydroxyethyl disulfide as a colorless oil, n 15765.

EXAMPLE 3 Compound 5464 1,2,2-trichloroethyl-2',3'-dihydroxypropyl disulfide When 100 grams 1,2,2-trichloroethyl sulfenyl chloride (0.5 M) were reacted at 2530 C. with 54 grams monothioglycerol (0.5M) in 50 ml. of Cl-lCl by Method l-A, 1,2,2-trichloroethyl-2,3-dihydroxypropyl disulfide was obtained in an 86 percent yield as an orange colored oil, n 1.5894.

EXAMPLE 4 Compound 6465 2,2,2-trichloroethyl-2,3- dihydroxypropyl disulfide.

The reaction of 185 grams 2,2,2-trichloroethyl sulfenyl chloride (0.925 M) at 20 C. with 100 grams monothioglycerol (0.925 M) in 100 grams of CI-lCl produced 2,2,2-trichloro-2,2'-dihydroxypropyl disulfide in a quantitative yield as a thick colorless oil that solidifies. mp. 4647 C.

EXAMPLE 5 Compound 6467 2,2-dichlorovinyl-B- hydroxyethyl disulfide When 48.3 grams 5607 (Ex. 2, 0.2 M) were dehydrochlorinated at 20-25 C. as described in Method LB with one equivalent of sodium ethoxide in 150 ml. of ethanol, 2,2-dichlorovinyl-B-hydroxyethyl disulfide was obtained in an 86 percent yield as a reddish oil, n 1.6145.

EXAMPLE 6 Compound 6466 2,2-dichlorovinyl-2',3'-dihydroxypropyl disulfide Reaction at 20-25 C. of one equivalent sodium ethoxide in 150 grams of ethanol with 54.3 grams 6465 (Ex. 4, 0.2 M) by Method l-B furnished 2,2-dichlorovinyl-2,3-dihydroxypropyl disulfide in a 90 percent yield as a reddish oil n 1.5930.

EXAMPLE 7 Compound 5420 1,2,2-trichloroethyldithioethy1-ethyl carbonate When 20 grams of 1,2,2-trichloroethyl sulfenyl chloride (0.1 M) were reacted at 3035 C. with 15.02 grams ethyl-2-mercaptoethyl-carbonate (0.1M) as described in Method II-C, using 100 ml. of CHCl as a solvent 1,2,2-trichloroethyldithioethyl-ethyl carbonate 5420 was obtained in a 97 percent yield as a faintly yellow oil, b l31-2 C., n,, 1.5346.

EXAMPLE 8 Compound 5422 2,2,2-trichloroethyldithioethylethyl carbonate 20 grams of 2,2,2-trichloroethyl sulfenyl chloride (0.1 M) when reacted at 3035 C. with 15.02 grams ethyl-2-mercaptoethyl-carbonate (0.1 M) as in Method II-C using 100 ml. of CHCl as a solvent furnished 2,2,2-trichloroethyldithioethyl-ethyl carbonate in a 96 percent yield as a peach colored oil, n 1.5263.

EXAMPLE 9 Compound 6463 1,1,2-trichloro-3,4-dithiaheptane- 6,7-di( ethyl carbonate) Reaction of27. 15 grams 5464 (0.1 M, Ex. 3) with 25 grams ethyl chloroformate (0.23 M, 15 percent excess) as described in Method lI-A furnished 1,1,2-trichloro- 3,4-dithiaheptane-6,7-di(ethyl carbonate) in a 94 percent yield as a yellow oil, n 1.5480.

EXAMPLE 10 Compound 6754 1,2,2-trichloroethyldithioethyl-S- ethyl thiol carbonate When 9.1 grams (0.03 M) 1,2,2-tn'chloroethyldithioethyl-chloroformate (Ex. 33) were reacted with a large excess of ethyl mercaptan (30 ml. in all) in the presence of 6.1 grams triethylamine at 25 C. as described in Method II-B, 1,2,2-trichloroethyldithioethyl-S-ethyl thiol carbonate was obtained in an 86 percent yield as a reddish oil, n 1.5624.

EXAMPLE 11 EXAMPLE 12 Compound 6464 1,1,2-trichloro-3,4-dithiaheptane- 6,7-di(ethylthiol carbonate) When 27.15 grams of 5464 (0.1 M, Ex. 3) were reacted with 30 grams ethyl chlorothiol formate (0.24 M, 20 percent excess) as described in Method lI-A, l ,1 ,2-trichloro-3,4-dithiaheptane-6,7-di(ethylthiol carbonate) was obtained in an percent yield as a dark yellow oil, n 1.5565.

EXAMPLE 13 Compound 6759 1,2,2-t1ichloroethyldithioethyl-S- ethyl dithiocarbonate Addition of 2.0 grams of Et N (0.02 M) to a mixture of 6.4 grams of 1,2,2-trichloroethyldithioethyl-thiono chloroformate (Ex. 38) (0.02 M) and 1.2 grams of ethyl mercaptan (0.02 M) in 25 ml of 3:1 benzenezpet. ether at 35 C. in Method II-B resulted in 1,2,2- trichloroethyldithioethyl-S-ethyl dithiocarbonate in a quantitative yield as an orange oil, n 1.5840.

EXAMPLE 14 Compound 5606 1,2,2-trichloroethyl dithioethylphenyl carbonate 24.15 grams of 5598 (0.1 M, Ex. 1) when reacted at 65 C (reflux) in II-A with 15.65 grams phenyl chloroformate (0.1M) in 50 ml. of Cl-lCl furnished 1,2,2-trichloroethyldithiosthyl-phenyl carbonate in an 81 percent yield as a yellow 011, n 1.5695.

EXAMPLE 15 Compound 6555 2,2,2-trichloroethyldithioethylphenyl carbonate Reaction of 24.15 grams 5607 (0.1 M, Ex. 2) with 17.65 grams phenyl chloroformate (0.113 M, 9 percent excess) at 114120 C. as described in [LA resulted in a quantitative yield of 2,2,2-trichloroethyldithioethylphenyl carbonate as a dark yellow oil, n 1.5632.

EXAMPLE 16 Compound 6554 1,2,2-trichloroethy1dithioethyl-S- phenyl thiol carbonate When 24.15 grams of 5598 (0.1 M, Ex. 1) were reacted with 19.25 grams of phenyl chlorothiol formate (0.112 M, 9 percent excess) at 115120 C in II-A,

1,2,2,-trichloroethyldithioethyl-S-phenyl thiol bonate was obtained in a 97 n 1.5967.

car-

EXAMPLE 17 Compound 6556 2,2,2-trichloroethyldithioethyl-S- phenyl thiol carbonate 24.15 grams of 5607 (0.1 M, Ex. 2) were reacted at 1l5120 C. as in [LA with 19.25 grams of phenyl chlorothiolformate (0.112 M, 9 percent excess), to ob-' tain 2,2,2-trichloroethyldithioethyl-S-phenyl thiol carbonate in a quantitative yield as a dark yellow oil, n 1.5932.

1 EXAMPLE 18 Compound 6808 2,2-dichlorovinyl dithioethylethyl carbonate Reaction of 5.35 grams of 2,2-dichlorovinyl dithioethyl chloroformate (Ex. 35) (0.02 M) with abpercent yield as a dark oil,

solute EtOH (50 ml.) at 80 C as described in Method II-B resulted in 2,2-dichlorovinyldithioethyl-ethyl carbonate in a quantitative yield as a dark oil, n 1.5740.

EXAMPLE 19 Compound 6553 2,2-dichlorovinyldithioethyl phenyl carbonate When 20.5 grams of 6467 (0.1 M, Ex. 5) were reacted with 17.65 grams of phenyl chloroformate (0.113 M, 9 percent excess) at 110-1l5 C. in II-A there was obtained 2,2-dichlorovinyldithioethyl phenyl carbonate in a quantitative yield as a dark oil, 11925 EXAMPLE 20 Compound 6755 bis-( 1,2,2-trichloroethyldithioethyl )-ca.rbonate When 9.1 grams of 1,2,2-trichloroethyldithioethyl chloroformate (0.03 M) were reacted in 100 ml. of CHC1 with 7.25 grams of 5598 (0.03 M, Ex. 1) at 30 C. in Method [LA in the presence of 3.1 grams of Et N (0.03 M), bis-(1,2,2-trichloroethyldithioethyl)-carbonate was obtained, after removal of Et N-HCl and heating at 115-20 C., as a dark oil in a 92 percent yield, n 1.5735.

EXAMPLE 21 Compound 6479 bis-(2,2,2-trichloroethyldithioethyl)-carbonate When 7 grams of 2,2,2-t1ichloroethyldithioethyl chloroformate (0.023 M) were reacted with 5.55 grams of 5607 (0.023 M, Ex. 2) at 115-125C. in lI-A, bis- (2,2,2-trichloroethyldithioethyl) carbonate was obtained in a 95 percent yield as a dark oil, n 1.5839.

EXAMPLE 22 Compound 6757 (1,2,2-trichloroethyldithioethyl)- 2,2-dichlorovinyldithioethyl) carbonate Reaction of 3 grams of 1,2,2-trichloroethyldithioethyl chloroformate (Ex. 33) (0.01 M) with 2 grams of 6467 (0.01 M, Ex. 5) in 50 ml. of benzene in the presence of 1 gram Et N (0.01 M) in 11-8 resulted in a 90 percent yield of (1,2,2-trichloroethyldithioethyl 2,2-dichlorovinyldithioethyl) carbonate as a brown oil.

EXAMPLE 23 EXAMPLE 24 Compound 5604 1,2,2-trichloroethyldithioethyl-N, N-diethyl carbamate When 24.15 grams of 5598 (0.1 M, Ex. 1) were reacted in 50 ml. of CHCl with 13.55 grams diethyl carbamoyl chloride (0.1 M) as described in III-B, 1,2,2- trichloroethyldithioethyl-N, N-diethyl carbamate was obtained in an percent yield as a faintly yellow oil, n 1.5413.

EXAMPLE 25 Compound 6810 2,2-dichlorovinyldithioethyl-N, N-

diethyl carbamate I Reaction of 5.35 grams of 2,2dichlorovinyldithioeth yl chloroformate (0.02 M) in 50 ml. of benzene with 2.92 grams of diethyl amine (0.04 M) at 25-30 C. in III-C resulted in 2,2-dichlorovinyldithioethyl-N, N- diethyl carbamate in a quantitative yield as a dark oil.

EXAMPLE 26 Compound 6451 l,2,2-trichloroethyldithioethyl-N- phenyl carbamate 24.15 grams of 5598 (0.1 M, Ex. 1) when reacted with 12 grams of phenyl isocyanate (0.1 M) at -95 C. as described in III-A furnished l,2,2-trichloroethyldithioethyl-N-phenyl carbamate in an 89 percent yield as a thick oil.

EXAMPLE 27 Compound 6452 2,2,2-trichloroethyldithioethyl-N- phenyl carbamate When 24.15 grams of 5607 (0.1 M, Ex. 2) were reacted with 12 grams of phenyl isocyanate (0.1 M) at 90-95 C. as in Ill-A 2,2,2-trichloroethyldithioethyl- N-phenyl carbamate was obtained in a 70 percent yield as a heavy oil.

EXAMPLE 28 Compound 6795 1,2,2-trichloroethyldithioethyl acetate Reaction of 24.15 grams of 5598 (0.1 M, Ex. 1) with 7.85 grams of acetyl chloride (0.1M) in 50 ml. of benzene at 80-85 C. as described in IV resulted in l,2,2-trichloroethyldithioethyl acetate in a 97 percent yield as a faintly yellow oil, n 1.5460.

EXAMPLE 29 Compound 6796 2,2,2-trichloroethyldithioethyl acetate When 24.15 grams of 5607 (0.1 M, Ex. 2) were reacted with 7.85 grams of acetyl chloride (0.1 M) in 50 ml. of benzene at 80-85 C. in Method IV, 2,2,2- trichloroethyldithioethyl acetate was obtained in a 95 percent yield as a faintly yellow oil, n 1.5440.

EXAMPLE 30 Compound 6797 2,2-dichlrovinyldithioethyl acetate 6.15 grams of 6467 (0.03 M, Ex. 5) when reacted with 2.36 grams of acetyl chloride (0.03 M) in 25 ml. of benzene at 8085 C. in IV, furnished 2,2- dichlorovinyldithioethyl acetate in a 95 percent yield as a dark oil, n 1.5808.

EXAMPLE 31 Compound 6758 1,2,2-trichloroethyl-2,3-diacetoxypropyl disulfide Reaction of 27.15 grams of 5464 (0.1 M, Ex. 3) with 17.7 grams of acetyl chloride (0.226 M, 12 percent excess) in 100 ml. of benzene at 40 C. as described in IV resulted in 1,2,2-trichloroethyl-2, 3-diacetoxypropyl disulfide in a 90 percent yield as a faintly yellow oil, n 1.5280.

EXAMPLE 32 Compound 6761 bis-( 2,2,2-tn'chloroethyldithioethyl)oxalate When 24.15 grams of 5607 (0.1M, Ex. 2) were reacted with 6.35 grams of oxalyl chloride (0.05 M) in 100 ml. of benzene at 35 C. as in IV, bis (2,2,2- trichloroethyldithioethyl oxalate was obtained in a 98 percent yield as a thick yellowish oil.

EXAMPLE 3 3 l,2,2-tricl'1loroethyldithioethyl chloroformate Allowing a mixture of 24.2 grams of 5598 (0.1 M, Ex. 1) and 12 grams of phosgene (0.121M, 20 percent excess) to stand at room temperature in 125 ml. dry benzene for three days, resulted in 1,2,2-trichlor0ethyldithioethyl chloroformate as a light yellow oil in a 92 percent yield, n 1.5530.

EXAMPLE 34 2,2,2-trichloroethyldithioethyl chloroformate Mixing 12.08 grams of 5607 (0.05 M, Ex. 2) with 7.5 grams of phosgene (0.0757 M, 50 percent excess) in 125 ml. of benzene under the same conditions as in Ex. 33 resulted in 2,2,2-trichloroethyldithioethyl chloroformate in a 96 percent yield as a light yellow oil.

EXAMPLE 35 2,2-dichlorovinyldithioethyl chloroformate Heating a mixture of 15 grams of 6467 (0.073 M, Ex. 5) and grams of phosgene (0.101 M, 70 percent excess) in 100 ml. dry benzene in a sealed tube at 80-85 C. and allowing to stand at room temperature overnight furnished 2,2-dichlorovinyldithioethyl chloroformate in a 95 percent yield as reddish oil, n 1.5915.

EXAMPLE 36 evidenced by the infrared scan to give 1,2,2- trichloroethyldithiopropyl-2 ,3 -di-( chloroformate EXAMPLE 37 2,2,2-trichloroethyldithiopropyl-2 ,3 -di-(chloroformate) Heating a mixture of 27.2 grams of 6465 (0.1 M, Ex. 4) and 24 grams of phosgene (0.242 M, 21 percent excess) in 100 ml. benzene, then removing the benzene and heating at C. and 0.05 mm. Hg. for 1 hour furnished 2,2,2-trichloroethyldithiopropyl2,3'-di- (chloroformate) in an percent yield as a yellow oil, n 1.5780.

EXAMPLE 3 8 l,2,2-trichloroethyldithioethyl-thiono chloroformate The chloroformate was prepared by reacting 24.16 grams 5598 (0.1 M, Ex. 1) with 12 grams of thiophosgene (0.103 M) in the presence of 10.1 grams of Et N (0.1 M) in 50 ml of benzene-petroleum ether (/:1). Removal of the solvent and heating the residue with an additional 6 grams of thiophosgene (0.05 M) furnished 1 ,2,2-trichloroethyldithioethyl thiono chloroformate in an percent yield as a red oil.

Example 39 The procedure of Example 14 was repeated, replacing the phenyl chloroformate by 0.1 mole of butyl chloroformate to produce 1,2,2-trichloroethyldithioethyl butyl carbonate.

Example 40 The procedure of Example 8 was repeated, replacing the ethyl-Z-mercaptoethyl-carbonate by 0.1 mole of methyl-Z-mercaptoethyl carbonate to produce 2,2,2- trichloroethyldithoethyl-methyl carbonate. EXAMPLE 41 The procedure of Example 28 was repeated, replacing the acetyl chloride by 0.1 mole of benzoyl chloride to produce 1,2,2-trichloroethyldithioethyl benzoate.

EXAMPLE 42 The procedure of Example 30 was repeated, replacing the acetyl chloride by 0.03 mole of p-chlorobenzoyl chloride to produce 2,2-dichlorovinyldithioethyl pchlorobenzoate.

EXAMPLE 43 The procedure of example 29 was repeated, replacing the acetyl chloride by 0.1 mole of butyryl chloride to produce 2,2,2-trichloroethyldithioethyl butyrate.

EXAMPLE 44 The procedure of example 28 was repeated, replacing the acetyl chloride by 0.1 mole of trichloroacetyl chloride to produce l,2,2-trichloroethyldithioethyl trichloroacetate.

EXAMPLE 45 The procedure of example 25 was repeated, replacing the diethyl amine with 0.04 mole of dimethyl amine to produce 2,2-dichlorovinyldithioethyl-N,N-dimethyl carbamate.

EXAMPLE 46 The procedure of example 24 was repeated, replacing the diethyl amine with 0.04 mole of dibutyl amine to produce 1,2,2-trichloroethyldithioethyl-N,N-dibutyl carbamate.

EXAMPLE 47 The procedure of Example 25 was repeated, replacing the diethyl amine with 0.04 mole of mono propyl amine to produce 2,2-dichlorovinyldithioethyl-N- propyl carbamate.

EXAMPLE 48 The procedure of Example 26 was repeated, replacing the phenyl isocyanate by 0.1 mole of a-naphthyl isocyanate to produce l,2,2-trichloroethyldithioethyl- N-a-naphthyl carbamate.

EXAMPLE 49 The procedure of Example 25 was repeated, replacing the diethyl amine by 0.04 mole of N-methyl aniline to produce 2,2dichlorovinyldithioethyl-N-phenyl-N- methyl carbamate.

EXAMPLE 50 The procedure of Example 25 was repeated, replacing the diethyl amine with 0.04 mole of diphenyl amine to produce 2,2-dichlorovinyldithioethyl-N,N-diphenyl carbamate.

EXAMPLE 1 The procedure of Example 25 was repeated, replacing the chloroformate with 0.01 mole of 1,2,2- trichloroethyldithiopropyl-2 ',3 -di-(chloroformate) to produce 1 1 ,2-trichloro-3 ,4-dithiaheptane-6,7-di- (N,N-diethyl carbamate).

EXAMPLE 52 The procedure of Example 36 was repeated, replacing Compound 5464 with 0.1 mole of Compound 6466 to produce 2,2-dichlorovinyldithiopropyl-2,3-di- (chloroformate).

EXLE 5 3 The procedure of Example 25 was repeated, replacing the diethyl amine by 0.04 mole of morpholine to produce 2,2-dichlorovinyldithioethyl morpholine carbamate.

EXAMPLE 54 The procedure of Example 25 was repeated, replacing the chloroformate by 0.02 mole of 2,2,2- trichloroethyldithioethyl chloroformate and the diethyl amine by 0.04 mole of piperidine to produce 2,2,2- trichloroethyldithioethyl-piperidyl carbamate.

EXAMPLE 55 The procedure of Example 32 was repeated, replacing the oxalylchloride by 0.05 mole phthalyl chloride to produce bis-(2,2,2-trichloroethyldithioethyl) phthalate.

EXAMPLE 56 The procedure of Example 32 was repeated, replacing Compound 5607 by 0.1 mole of Compound 6467 and replacing the oxalyl chloride by 0.05 mole of succinyl chloride to produce bis-(2,2-dichlorovinyldithioethyl) succinate.

EXAMPLE 57 The procedure of Example 32 was repeated, replacing the oxalyl chloride by maleyl chloride to produce bis-(2,2,2-trichloroethyldithioethyl) maleate.

EXAMPLE 5 8 EXAMPLE 5 9 Reaction of 12.0 grams (0.1 M) of Compound 5598 with 9.1 grams (0.05 M) of trichloroacetyl chloride in 50 ml. of dry benzene at 50C. gave a 91 percent yield of 1,2,2-trichloroethyldithioethyl trichloroacetate (Compound 7279) as a dark oil, n 1.5550.

E u I'LE 60 Reaction of 24. 15 grams (0.1 M) of Compound 5598 with 14.06 grams (0.1 M) of benzoyl chloride in 100 ml. of dry benzene at C. furnished 1,2,2- trichloroethyldithioethyl benzoate (Compound 7109) as a dark yellow oil in a yield of 92 percent.

ELE 61 Reaction of 24. 15 grams (0.1 M) of Compound 5598 with 16.7 grams (0.1 M) of cinnamoyl chloride in ml. of dry benzene at 85 C. gave a quantitative yield of 1,2,2-trichloroethyldithioethyl cinnamate (Compound 71 10) as an orange-yellow oil.

EXAMPLE 62 Reaction of 12.0 grams (0.05 M) of Compound 5598 with 8.53 grams of phenoxyacetyl chloride in 50 ml. of dry carbon tetrachloride at 80 C. gave a 96 percent yield of l,2,2-trichloroethyldithioethyl phenoxyacetate (Compound 7280) as a yellow oil.

EXAMPLE 63 12.0 grams (0.05 M) of 1,2,2-trichloroethyl-B- hydroxyethyl disulfide (Compound 5598) were reacted with 10.95 grams (0.05 M) of 2-methyl-4- chlorophenoxyacetyl chloride in 50 ml. of dry carbon tetrachloride at 80 C. to give a 99 percent yield of 1 ,2,2-trichloroethyldithioethyl-2-methyl-4'- chlorophenoxyacetate as a yellow oil.

EXAMPLE 64 Reaction of 24.15 grams (0.1 M) of 2,2,2- trichloroethyl-B-hydroxyethyl disulfide (Compound 5607) with 11.3 grams (0.1 M) of chloroacetyl chloride in 100 ml. of dry benzene at 85 C. gave 2,2,2- trichloroethyldithioethyl chloroacetate (Compound 7204) in a quantitative yield as a yellow oil, n 1.5516.

EXAMPLE 65 Reaction of 24. grams (0.1 M) of Compound 5607 with 14.06 grams (0.1 M) of benzoyl chloride in 100 ml. of dry benzene at 85 C. gave a 97 percent of 2,2,2- trichloroethyldithioethyl benzoate (Compound 7205) as a dark yellow oil, n 1.5760.

EXAMPLE 66 24.15 grams (0.1 M) of Compound 5607 were reacted with 16.7 grams (0.1 M) of cinnamoyl chloride in 100 ml. of dry benzene at 85 C. to give an 89 percent yield of 2,2,2-trichloroethyldithioethyl cinnamate (Compound 7206) as a yellow oil, n 1.6020.

EXAMPLE 67 Reaction of 14.6 grams (0.0712 M) of 2,2- dichlorovinyl-B-hydroxyethyl disulfide (Compound 6467) with 8.05 grams (0.0712 M) of chloroacetyl chloride in 100 ml. of dry benzene at 85 C. gave a 99 percent yield of 2,2-dichlorovinyldithioethyl chloroacetate (Compound 7201) as a dark oil, n 1.5685.

EXAMPLE 68 Reaction of 13.3 grams (0.065 M) of Compound 6467 with 9.15 grams (0.065 M) of benzoyl chloride in 100 ml. of dry benzene at 85 C. gave an 89 percent yield of 2,2-dichlorovinyldithioethyl benzoate (Compound 7202) as a dark oil, n 1.5915.

EXAMPLE 69 Reaction of 12.25 grams (0.0597 M) of Compound 6467 with 9.95 grams (0.597 M) of cinnarnoyl chloride in 100 ml. of dry benzene at 85 C. gave a quantitative yield of 2,2-dichlorovinyldithioethyl cinnamate (Compound 7203) as a dark oil, n 1.6240.

EXAMPLE 70 There can also be added surface active agents or wetting agents and/or inert solids in the liquid formulations. In such case, the active ingredient can be from 0.01 to 95 percent by weight of the entire composition.

As organic solvents there can be employed hydrocarbons, e.g., benzene, toluene, xylene, kerosene, diesel fuel, fuel oil, and petroleum naphtha, ketones such as acetone, methyl ethyl ketone and cyclohexanone, chlorinated hydrocarbons such as carbon tetrachloride, chloroform, trichloroethylene, and perchloroethylene, esters such as ethyl acetate, amyl acetate and butyl acetate, ethers, e.g., ethylene glycol monomethyl ether and diethylene glycol monomethyl ether, alcohols, e.g., methanol, ethanol, isopropanol, amyl alcohol, ethylene glycol, propylene glycol, butyl carbitol acetate and glycerine. Mixtures of water and organic solvents, either as solutions or emulsions, can be employed.

The novel products can also be applied as aerosols, e.g., by dispersing them in air by means of a compressed gas such as dichlorodifluoromethane or trichlorofluoromethane and other Freons and Genetrons, for example.

The products of the present invention can also be applied with adjuvants or carriers such as talc, pyrophyllite, synthetic fine silica, attapulgus clay, kieselguhr, chalk, diatomaceous earth, lime, calcium carbonate, bentonite, fullers earth, cottonseed hulls, wheat flour, soybean flour, pumice, tripoli, wood flour, walnut shell flour, redwood flour andlignin.

As stated, it is frequently desirable to incorporate a surface active agent in the compositions of the present invention. Such surface active or wetting agents are advantageously employed in both the solid and liquid compositions. The surface active agent can be anionic, cationic or nonionic in character.

Typical classes of surface active agents include alkyl sulfonate salts, alkylaryl sulfonate salts, alkylaryl polyether alcohols, fatty acid esters of polyhydric alcohols and the alkylene oxide addition products of such esters, and addition products of long chain mercaptans and alkylene oxides. Typical examples of such surface active agents include the sodium alkylbenzene sulfonates having 10 to 18 carbon atoms in the alkyl group, alkylphenol ethylene oxide condensation products, e.g., p-isooctylphenol condensed with 10 ethylene oxide units, soaps, e.g., sodium stearate and potassium oleate, sodium salt of propyl-naphthalene sulfonic acid, di (2-ethylhexyl) ester of sodium sulfosuccinic acid, sodium lauryl sulfate, sodium decane sulfonate, sodium salt of the sulfonated monoglyceride of coconut fatty acids, sorbitan sesquioleate, lauryl trimethyl ammonium chloride, octadecyl trimethyl ammonium chloride, polyethylene glycol lauryl ether, polyethylene glycol esters of fatty acids and rosin acids, e.g.,Ethofat 7 and 13, sodium N-methyl-N-oleyl taurate, Turkey Red Oil, sodium dibutyl naphthalene sulfonate, sodium lignin sulfonate, polyethylene glycol stearate, sodium dodecylbenzene sulfonate, tertiary dodecyl polyethylene glycol thioether (Nonionic 218), long chain ethylene oxide-propylene oxide condensation products, e.g., Pluronic 61 (molecular weight 1,000), polyethylene glycol ester of tall oil acids, sodium octyl phenoxyethoxyethyl sulfate, tris (polyoxyethylene) sorbitan monostearate (Tween and sodium dihexyl sulfosuccinate.

The spore germination tests were carried out as follows. A 1 percent suspension of the compound to be tested in water was prepared and there was also C. ulmi The solid and liquid formulations can be prepared by any of the conventional procedures. For example, the

., trees, cotton plants, wheat prepared a solution of agar in the water. The suspension was appropriately diluted with water and mixed with the agar solution to give the indicated concentrations of compounds in ppm. 0.3 ml. of the agar material was placed on a microscope slide and a film allowed to 10 form and solidify. Spores of Alternaria or Ustilago were dusted on the slides and they were placed in Petri dishes with filter paper and incubated at room temperature for 24 hours and the non germinated spores registered, 10 indicating 100 percent non germination in Table 2.

The foliage fungicide tests were carried out with COL infested cucumber leaves.

in 3 wi an equ wei t o e test compoun an attapu gus clay. The mixture was blended with soil infested with indicated organism and allowed to stand for 24 hours. Then the blend was spread evenly over a wet paper towel and 50 pea seeds were placed on the soil. The towels were rolled up and put in metal cans and stored at F. for 5 days and then at F. for 4 days. The cans were then removed and the rate of fungus Collectotrichum obiculare growth recorded, with 10 indicating no growth.

lycopmec' In Table 4 and the saprophytic portion of Table 9 the Helminthosporium sativum 30 compounds were tested as nematocides using water as z g'i the medium with Panagrellus and Rhabditis spp. at Ceratocystis ulmi room temperature. The less active compounds require Pythium ineg la rates above the 400 ppm. maximum used in Table 9. gfiifffgfi'f Many of the compounds also are useful as nematopounds per acre 5 cides against parasitic nematodes such as Meloidogyne spp. as shown in Table 9 as well as against other root knot nematodes. Rates above 200 ppm. are required for the less active compounds.

TABLE l.AGAR PLATES Organism at p.p.m.

Col Fus H01 Rhiz Vcrt In the Table the following abbreviations are used:

COL FUS F. N. HEL RHIZ VERT C. ULMI PY Ph pp No./A

In Tables 1 and 7 potato dextrose agar was used in the agar plate tests.

Ex. N o.

The biological testing results are complied in the following tables. In Tables 1, 2, 3, 7 and 8 a 0-10 scale is employed with 0 indicating no inhibition and 10 in- Code N 0.

compounds of the present invention can be applied to soil, growing plants, e.g

and other grain plants, vegetable plants, seeds, fabrics, 5 etc., to give pesticidal protection or can be applied to mature cotton beans, tomatoes, or other leafy plants to give defoliation or desiccant action.

dicating complete inhibition. In Table 4 and the saprophytic nematode portion of Table 9 the tabulation is expressed as percent non-motility after a 4 day incubation period. The blank no motility rate was 10 percent. In Tables 4, l0 ll, 12 and in the desiccation part of Tables 6 and 13 is given as actual percent defoliation. In the parasitic 20 nematode part of Table 9 the severity of root knots on tomato plants planted in soil infested with Meloidogyne spp. is indicated on a 0-10 scale where 0 indicates severe knotting and 10 indicates freedom from knots.

0880 055050800000500500 0 505 lm w l. 1 1 1 1 11 11 000 000080000000008000005 m m 11mm m 1111 111 111 1111 In Table 2 the spore germination tests were carried As shown in Tables 5, l0 and 12 the compounds exout with altemaria spp. and Ustilago and the foliage hibited some post emergent herbicide activity. While fungicide tests with Collectotrichum Obiculare. many of the compounds did not exhibit any significant 1 Higher rate is 1,000 p.p.m.

the lowest test rates. Because of the effectiveness of the compounds in the primary soil fungicide test in Table 8 some of the compounds were subjected to a secondary soil fungicide screening.

In the defoliant-desiccant tests, Compound 6467 did not show defoliation at the low rates employed in Table 6 but surprisingly showed very good desiccation. This can be taken advantage of in Texas and other areas where it is necessary to desiccate cotton prior to picking.

TABLE .L-SPORE (lERMlNA'll()N-FOLIAUE FUNGICIDE Organism at mun.

I Altvrnurin Ultilagn (ullrlnlrichmu nhivulnrr Ex. Code N0. No. 1,000 l 10 1.000 100 10 1.000 100 50 10 55JH. l 0 0 .1 l0 l0 0 3 l0 l0 0 4 l0 5 0 5 l0 0 0 0 l0 l0 0 7 l0 l0 8 8 10 K 3 0 l0 5 0 0 5 10 5 0 0 5 0 11 10 5 0 l0 0 12 10 5 0 10 5 13 8 0 0 5 0 14 0 0 0 0 0 15 5 0 0 5 0 1G 10 5 0 l0 0 l7 5 0 0 5 0 18 0 0 0 0 0 l9 l0 5 0 0 0 20 10 8 0 l0 5 21 O 0 0 10 10 22 10 8 0 l0 5 '23 8 0 0 5 0 24 10 8 8 10 10 25 0 0 0 0 0 2G 10 0 0 10 0 27 5 0 O 0 0 28 8 5 0 8 0 20 8 5 0 X 0 30 5 0 0 5 0 31 10 H 0 l0 5 3'1 5 0 0 0 0 TABLE 3.SOIL FUNGTCIDE Organism ly nt#/a. Fu at p.p.m. Rhiz at p.p.m. Vcrt. at p.p.ni. x. Code No. No. 200 500 10 500 100 10 500 100 10 1 0 0 10 2 10 0 O 3 l0 5 0 4 l0 0 0 5 10 5 0 ii 10 10 10 7 0 8 8 8 7 10 10 0 10 10 10 10 3 0 8 l1 6 8 0 12 10 5 8 13 J 0 8 14 10 8 8 l5 4 0 8 l0 8 8 8 17 0 2 5 l8 0 0 0 l.) 7 5 5 20 .I 10 10 ll 4 0 0 22 8 10 10 23 6 0 10 34 10 8 10 25 0 0 0 20 J 5 0 27 (i 0 0 28 10 0 l0 2.) 7 0 10 30 ii 0 0 31 \i 8 h 32 0 0 5 TABLE 7.AGAR PLATES Organism at p.p.m.

C. ulmi Col Fus RN. H01 Rlilz Von Code NO. Ex. 500 100 10 500 100 10 500 100 10 500 100 10 500 100 10 500 100 10 500 100 10 58 8 8 5 10 10 5 10 10 10 8 10 5 10 10 5 10 0 0 59 10 5 5 1O 10 5 1O 10 0 10 10 5 10 5 5 10 0 0 l0 5 .3 60 8 5 5 10 10 5 8 5 0 8 5 2 8 8 5 8 8 5 10 5 .1 61 5 2 0 10 10 5 5 2 0 8 8 5 8 8 5 5 5 2 8 0 0 62 10 10 5 10 10 5 10 5 0 10 10 5 1O 10 5 8 5 0 10 S S 63 10 10 5 10 10 5 5 5 0 8 5 2 8 5 2 5 B 0 10 5 0 64 8 5 0 10 8 5 10 5 0 8 5 0 10 5 5 l0 2 0 10 0 0 65 8 5 0 8 5 2 8 2 0 5 2 0 10 5 0 2 0 0 5 0 0 66 8 5 0 8 5 O 8 5 0 5 2 0 10 5 2 5 0 0 5 0 0 67 10 10 8 10 10 5 1O 1O 5 10 10 5 10 8 5 10 5 0 10 5 0 68 10 8 5 10 10 5 10 8 2 10 8 5 10 5 5 1O 5 0 10 2 0 69 5 2 0 5 5 2 5 2 0 8 5 0 5 5 2 2 0 0 2 0 0 70 10 5 0 10 8 5 10 5 0 10 8 0 10 5 2 5 0 0 l0 0 0 TABLE 8 TABLE 9 Soil Fungicidc (PY) Ncmatocide (at ppm.)

Saprophytic Parasitic At NO'IA Code No. Ex. No. 400 200 200 20 Primary Secondary Code No. Ex. No. 200 50 50 25 12.5 25 7108 58 l0 l0 l0 0 0 7279 5 9 80 i0 l 0 O 7109 60 I00 10 0 0 7108 58 g g 7 7 7 7110 6i 1o 10 l0 0 0 7279 59 7 7 7 6 5 7280 62 so so 1o 10' s 7109 60 7 5 7221 63 100 100 so 61 7 4 7204 64 100 100 so 10 0 62 9 6 5 5 6 30 7205 so 10 10 8.8 o 7231 63 7206 so so 10 1o 10 o 7204 64 8 5 7201 67 100 100 so 10' 0 7205 65 3 0 7202 68 so so 10 10* 0 gig? 2g 3 g 7203 69 so 10 1o 5 0 Indicates phytotoxic TABLE 10.--PRE- AND POST-EMERGENI IIERBICIDE Plant at #/a.

Oats Sugar beets Radish Flax Millet Pre Post Pre Post Pre Post Pre Post Pre Post Code N0. EX. 20 10 8 2 20 10 8 2 20 10 8 2 20 10 8 2O 10 8 2 58 3 0 4 7 5 5 8 3 6 3 3 5 0 0 4 59 5 5 4 1 3 5 l0 6 5 (i 0 4 2 3 7 4 9 9 7 4 60 2 3 3 10 4 6 4 0 4 0 0 5 0 0 3 61 6 3 4 8 2 5 10 0 4 10 0 3 0 0 3 62 3 3 3 3 3 0 G 3 7 5 4 3 3 3 5 1 2 0 3 3 63 9 8 0 0 10 10 J 7 10 10 0 3 10 10 9 7 10 1O 8 5 64 5 1 4 4 1 1 (i 7 1 0 6 6 4 0 8 G 0 0 1 1 65 1 1 1 1 1 0 2 3 O 0 1 1 0 0 1 0 0 0 0 0 66 4 0 2 1 0 0 1 0 3 2 0 0 4 0 0 0 0 0 1 0 67 6 0 4 3 0 0 7 G 0 0 5 4 6 2 6 6 4 0 2 2 68 6 5 4 3 3 0 10 6 5 0 3 3 5 2 6 3 0 0 3 1 69 0 0 1 1 0 0 10 10 0 0 4 4 4 0 3 4 0 0 1 2 70 4 5 1 0 3 l 3 1 0 0 2 1 O 0 3 1 1 0 1 0 1 Pro-emergent rates were 15 and 5 #/:1.

TABLE 11.-SECONDARY PRE-EMERGENT HERBICIDE Plant Soy- Water Johnson Wild Sugar Morning Code N 0. Ex. No. #/a. beans Cotton Corn Millet grass grass Pigweed mustard beets glory 7281 63 8 9 9 5 7 0 9 9 0 9 10 4 9 J 3 G 6 7 9 f) 8 9 2 0 7 2 2 5 6 6 8 7 4 TABLE 12.SECO NDARY POST-EMERGENT IIERBICIDE Plant Morn in g glory Sugar bu ts Water Johnson Wild grass grass ligwuod mustard Millet Corn Soy- #/a. beans Cotton Ex. No.

Code No.

TABLE 13 wherein A is selected from the group consisting of di to Defoliant DeSiccam I tetrahaloethyl and d1 to trihalovinyl and X is oxygen or sulfur and all halogen atoms have an atomic weight of 20 35 t 80.

2. A compound according to claim 1 wherein X is oxygen.

3. A compound according to claim 2 which is bis l ,2,2-trichloroethyl dithioethyl)-carbonate.

4. A compound according to claim 2 which is bis (2,2,2-trichloroethyl dithioethyl)-carbonate.

5. A compound according to claim 2 which is his (2,2-dichlorovinyl dithioethyl)-carbonate.

6. A compound according to claim 2 which is 30 (trichloroethyldithioethyl)-(2,2-dichlorovinyl- 2 13l4 l0 27 30 0 04 0 M 3 4824 30 m .w s 6 D89 4 6622 2 000000 00 5 2 Ill.

dithioethyl) carbonate.

We claim: 7. A compound according to claim 6 which is 1,2,2,- 

2. A compound according to claim 1 wherein X is oxygen.
 3. A compound according to claim 2 which is bis (1,2,2-trichloroethyl dithioethyl)-carbonate.
 4. A compound according to claim 2 which is bis (2,2,2-trichloroethyl dithioethyl)-carbonate.
 5. A compound according to claim 2 which is bis (2,2-dichlorovinyl dithioethyl)-carbonate.
 6. A compound according to claim 2 which is (trichloroethyldithioethyl)-(2,2-dichlorovinyldithioethyl) carbonate.
 7. A compound according to claim 6 which is (1,2,2,-trichloroethyldithioethyl)-(2,2-dichlorovinyldithioethyl) carbonate. 